KR20220154144A - Zirconium phosphate particles, basic gas deodorant using the same, and manufacturing method thereof - Google Patents

Abstract

Zirconium phosphate particles obtained by bringing α-zirconium phosphate particles into contact with a basic liquid having a pH of 9 or higher and further contacting an acidic liquid with a pH of 6 or lower, or 3 L of air containing 10 mg of zirconium phosphate particles and 1000 ppm of ammonia gas A zirconium phosphate particle whose ammonia gas reduction rate in the test bag containing the zirconium phosphate particle after being placed in a test bag at normal temperature and normal pressure and left for 10 minutes is 50% or more.

Description

Zirconium phosphate particles, basic gas deodorant using the same, and manufacturing method thereof

The present invention relates to zirconium phosphate particles and a particulate basic gas deodorant using the same, a deodorant for textiles, a composition for deodorizing processing, a deodorizing resin composition, and a deodorizing fiber, and belongs to the field of adsorbent technology, deodorant technology, and resin and fiber technology.

In recent years, amid the demand for safer and more comfortable living environments, deodorizing sheets, deodorizing curtains, and deodorizing filters for the purpose of adsorbing and deodorizing harmful and odorous gases, and deodorizing functions for sweat odor, old age odor, fatigue odor, etc. , 'deodorant products' such as clothing and bedding have been released.

As representative gases to be adsorbed and to be deodorized, acidic gases such as acetic acid, basic gases such as ammonia, sulfur-based gases such as methyl mercaptan, aldehyde-based gases such as formaldehyde, ketone-based gases such as acetone, etc. are known, respectively. Development of deodorant and deodorant products suitable for the gas of In recent years, attention has been paid to basic gas adsorbents and basic gas deodorizing products that can adsorb basic gases such as ammonia, which are the cause of sweat odor and fatigue, and use inorganic solid acids such as zirconium phosphate as basic gas adsorbents. In addition, deodorant products that are supported or kneaded on fibers are being developed.

For example, in order to deodorize the smell of sweat or blood, the development of clothing using deodorant fibers has been studied, but for this purpose, it has been required to deodorize basic gases such as ammonia, which are the causative substances, as quickly as possible. .

In Japanese Patent No. 3896327, an ammonia gas adsorption filter containing 0.5 to 4 parts by weight of alpha-type zirconium phosphate based on 1 part by weight of fibrillated fibers and having a propylene glycol monomethyl ether acetate decomposition rate of less than 4% is disclosed.

Japanese Unexamined Patent Application Publication No. 2018-178313 discloses a deodorant for textile containing α-zirconium phosphate having a median diameter of 0.2 to 0.7 μm as particle diameter, a maximum particle diameter of 5.0 μm or less, and a D ₁₀ diameter of 0.1 μm or more. has been

However, in the filter for adsorption of ammonia gas disclosed in Japanese Patent No. 3896327, 2.34 parts by weight of α-type zirconium phosphate having an average particle diameter of 0.9 μm is blended with 1.0 part by weight of the fibril compound of aramid fibers to form a flat plate-shaped adsorption filter. was manufactured, and in order to achieve sufficient high-speed deodorization performance, it was necessary to use a large amount of α-type zirconium phosphate for fibers. In addition, it is not practical to apply the present technology to deodorizing textiles or deodorizing clothing.

In addition, the deodorant fiber described in Japanese Unexamined Patent Publication No. 2018-178313 improves spinnability and deodorization by controlling the particle diameter of the deodorant to be kneaded and added to the fiber to a certain value or less, but problems related to high-speed deodorization And there was no mention or suggestion about the solution.

According to one embodiment of the present invention, zirconium phosphate particles having high deodorization performance against basic gases such as ammonia and trimethylamine, and particularly excellent deodorization rate of ammonia, a deodorant using the same, a composition for deodorizing processing, a deodorizing resin composition, and deodorizing fibers, And it makes it a subject to provide those manufacturing methods.

The present invention includes the aspects of the following [1] to [21].

[1] Zirconium phosphate particles obtained by bringing α-zirconium phosphate particles into contact with a basic liquid having a pH of 9 or higher and further contacting an acidic liquid with a pH of 6 or lower.

[2] The zirconium phosphate particle according to [1], wherein the basic liquid contains an alkali metal and/or an alkaline earth metal.

[3] After putting 10 mg of zirconium phosphate particles and 3 L of air containing 1000 ppm of ammonia gas into a test bag at room temperature and normal pressure and leaving it for 10 minutes, in the test bag containing the zirconium phosphate particles, expressed by the following formula (1) Zirconium phosphate particles having an ammonia gas reduction rate (X; unit %) of 50% or more.

X={(A ₀ -A ₁ )/A ₀ )}×100 (1)

[In Equation (1), A ₀ means the ammonia gas concentration of the test bag containing no zirconium phosphate particles, and A ₁ means the ammonia gas concentration of the test bag containing zirconium phosphate particles.]

[4] The zirconium phosphate particle according to any one of [1] to [3], wherein the median diameter of the primary particles is 0.1 to 10 μm.

[5] The zirconium phosphate particle according to any one of [1] to [4], wherein the reduced drying fraction (Y; unit weight%) represented by the following formula (2) after heating at 150°C for 2 hours is 5.0% by weight or less. .

Y={(B ₀ -B ₁ )/B ₀ ｝×100 (2)

[In Formula (2), B ₀ means the weight of zirconium phosphate particles before heating, and B ₁ means the weight of zirconium phosphate particles after heating.]

[6] A basic gas deodorant containing the zirconium phosphate particles according to any one of [1] to [5].

[7] A basic gas deodorizer for textiles containing the zirconium phosphate particles according to any one of [1] to [5].

[8] A basic gas deodorizer for fiber kneading containing the zirconium phosphate particles according to any one of [1] to [5].

[9] A composition for basic gas deodorizing processing containing the zirconium phosphate particles according to any one of [1] to [5].

[10] A basic gas deodorizing resin composition containing the zirconium phosphate particles according to any one of [1] to [5].

[11] A basic gas deodorizing fiber comprising the zirconium phosphate particles according to any one of [1] to [5].

[12] The basic gas deodorizing fiber according to [11], comprising at least one fiber selected from the group consisting of polyester, polyurethane, nylon, rayon, cotton, acrylic, aramid, vinylon, polyethylene and polypropylene.

[13] The zirconium phosphate particle according to any one of [1] to [5], which includes contacting the α-zirconium phosphate particle with a basic liquid having a pH of 9 or higher and further contacting an acidic liquid with a pH of 6 or lower. manufacturing method.

[14] The method for producing zirconium phosphate particles according to [13], wherein the basic liquid contains an alkali metal and/or an alkaline earth metal.

[15] A method for producing a basic gas deodorizing resin composition comprising mixing zirconium phosphate particles obtained by the production method according to [13] or [14] and a resin.

[16] contacting zirconium phosphate particles with a basic liquid having a pH of 9 or higher and then further contacting an acidic liquid with a pH of 6 or lower to obtain liquid-treated zirconium phosphate particles, and mixing the liquid-treated zirconium phosphate particles and a resin. A method for producing a basic gas deodorizing resin composition.

[17] A method for producing a basic gas deodorizing fiber comprising spinning the basic gas deodorizing resin composition obtained by the production method described in [15] or [16].

[18] A method for producing a basic gas deodorizing resin composition comprising contacting a resin containing zirconium phosphate particles with a basic liquid having a pH of 9 or higher and then contacting with an acidic liquid with a pH of 6 or lower.

[19] The method for producing the basic gas deodorizing resin composition according to [18], wherein the zirconium phosphate particles are those according to any one of [1] to [5].

[20] A method for producing a basic gas deodorizing fiber comprising contacting a fiber containing zirconium phosphate particles with a basic liquid having a pH of 9 or higher and then contacting an acidic liquid with a pH of 6 or lower.

[21] The method for producing a basic gas deodorizing fiber according to [20], wherein the zirconium phosphate particles are those according to any one of [1] to [5].

According to one embodiment of the present invention, zirconium phosphate particles having high deodorization performance against basic gases such as ammonia and trimethylamine, and particularly excellent deodorization rate of ammonia, a deodorant using the same, a composition for deodorizing processing, a deodorizing resin composition, and a deodorizing fiber, and methods for their preparation are provided.

Hereinafter, the present disclosure will be described in detail.

In addition, in this specification, unless otherwise specified, '%' means 'weight%', 'part' means 'parts by weight', and 'ppm' means 'volume ppm'.

Further, in the present specification, description of 'lower limit to upper limit' indicating a numerical range indicates 'more than the lower limit and less than or equal to the upper limit', and description of 'upper limit to lower limit' indicates 'less than the upper limit and more than the lower limit'. That is, it represents a numerical range including upper and lower limits.

In addition, in the present specification, 'room temperature' means 25 ± 5 ℃.

In addition, about this indication, the combination of two or more of the preferable aspects mentioned later is also a preferable aspect.

The zirconium phosphate particles in the present disclosure are particles containing zirconium phosphate as a main component, and may contain impurities and moisture derived from raw materials and manufacturing processes. The main component is 50% by weight or more of the zirconium phosphate component contained in the particles, preferably 80% by weight or more, more preferably 90% by weight or more, still more preferably 95% by weight or more.

1. Zirconium Phosphate Particles

In the zirconium phosphate particles related to the first aspect of the present disclosure, α-zirconium phosphate particles are brought into contact with a basic liquid having a pH of 9 or higher (hereinafter, simply referred to as 'basic liquid'), and then further acidic liquid with a pH of 6 or lower (hereinafter, It is simply a zirconium phosphate particle obtained by contacting it with 'acidic liquid').

The zirconium phosphate particles related to the second aspect of the present disclosure are prepared by putting 10 mg of zirconium phosphate particles and 3 L of air containing 1000 ppm of ammonia gas into a test bag at room temperature and normal pressure and leaving the test bag for 10 minutes, and then containing the zirconium phosphate particles. It is a zirconium phosphate particle whose ammonia gas reduction rate (X; unit %) represented by Formula (1) below is 50% or more.

X={(A ₀ -A ₁ )/A ₀ )}×100 (1)

[In formula (1), A ₀ means the ammonia gas concentration of the test bag containing no zirconium phosphate particles, and A ₁ means the ammonia gas concentration of the test bag containing zirconium phosphate particles.]

In addition, in the present specification, 'the zirconium phosphate particle of the present disclosure' includes the zirconium phosphate particle related to the first aspect and the zirconium phosphate particle related to the second aspect.

1-1. Zirconium phosphate particles related to the first aspect

The zirconium phosphate particles related to the first aspect are zirconium phosphate particles obtained by bringing α-zirconium phosphate particles into contact with a basic liquid and then further bringing them into contact with an acidic liquid.

Hereinafter, a basic liquid, an acidic liquid, α-zirconium phosphate particles as a raw material, and a method for producing zirconium phosphate are described.

1-1-1. basic liquid

The base contained in the basic liquid is not particularly limited, and known bases including, for example, alkali metals, alkaline earth metals, ammonia, amines, and ammonium salts can be used. Examples of the alkali metal include lithium, sodium and potassium, examples of the alkaline earth metal include magnesium and calcium, and examples of the amine include alkyl amines such as methylamine, dimethylamine and trimethylamine, aniline, and phenyl Arylamines, such as methylamine, and heterocyclic aromatic amines, such as pyridine, are mentioned, Tetramethylammonium hydroxide etc. are mentioned as an ammonium salt. These may be used individually by 1 type, and may use 2 or more types together.

Among these, it is preferable to use a base containing an alkali metal and/or alkaline earth metal because of its strong basicity, efficient contact treatment with a basic liquid, and almost no odor and good working environment. do. Examples of bases containing an alkali metal include lithium hydroxide, sodium hydroxide and potassium hydroxide, and examples of bases containing an alkaline earth metal include magnesium hydroxide and calcium hydroxide.

The solvent used for the basic liquid having a pH of 9 or higher is not particularly limited, but is preferably water and lower alcohols such as methanol, more preferably water. The method for preparing the basic liquid having a pH of 9 or higher is not particularly limited, and known methods can be applied. For example, a base containing an alkali metal and/or an alkaline earth metal, specifically, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, or the like, tetramethylammonium hydroxide, etc. is dissolved in a solvent such as water. Can be prepared by dissolving

The pH of the basic liquid is not particularly limited as long as it satisfies 9 or higher, but is preferably pH 12 or higher, more preferably pH 13 or higher, from the viewpoints of efficiency of the manufacturing process and resource saving.

In addition, the total amount of bases such as alkali metals and/or alkaline earth metals when the α-zirconium phosphate particles are brought into contact with a basic liquid is a hydroxyl group bound to the phosphorus atom of the α-zirconium phosphate (hereinafter referred to as 'P-OH group '), preferably at least 1/20 molar ratio, more preferably at least 1/10 molar ratio, and still more preferably at least 1/5 molar ratio. If the molar ratio is 1/20 or more, the effect of imparting high-speed deodorization to α-zirconium phosphate can be sufficiently obtained.

1-1-2. acid liquid

The acid used for the acidic liquid is not particularly limited, but known acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid are exemplified. An acid having an acid dissociation index (i.e., pKa) smaller than that of the phosphoric acid group of α-zirconium phosphate is preferable.

The solvent used for the acidic liquid is not particularly limited, but is preferably water and lower alcohols such as methanol, more preferably water.

The pH of the acidic liquid is not particularly limited as long as it satisfies 6 or less, but is preferably pH 2 or less, more preferably pH 1 or less, from the viewpoint of efficiency of the manufacturing process and resource saving.

In addition, the total amount of acid at the time of contacting the zirconium phosphate particles with an acidic liquid is preferably 100 mol% or more relative to the amount of P-OH groups in the α-zirconium phosphate before contacting with a basic liquid having a pH of 9 or higher. Preferably it is 300 mol% or more, More preferably, it is 1000 mol% or more. If it is 100 mol% or more, the effect of imparting high-speed deodorization to α-zirconium phosphate can be sufficiently obtained.

1-1-3. α-Zirconium Phosphate Particles

As α-zirconium phosphate as a raw material used in the production of zirconium phosphate related to the first aspect, various compounds can be used, and conventionally well-known α-zirconium phosphate can be used.

Although various compounds can be used as α-zirconium phosphate, a compound represented by the following formula (3) and having a cation exchange capacity per unit weight of 6.7 meq/g is preferable.

Zr _1-x Hf _x H _a (PO ₄ ) _b nH ₂ O (3)

In equation (3), a and b are integers satisfying 3b - a = 4, b is 2.0 < b ≤ 2.1, x is an integer of 0 ≤ x ≤ 0.2, and n is an integer of 0 ≤ n ≤ 2.0. .

In the formula (3) of α-zirconium phosphate, hafnium (Hf) is derived from the raw material zirconium compound. x in formula (3) is an integer of 0≤x≤0.2. In the present disclosure, preferably 0≤x≤0.2, more preferably 0.005≤x≤0.1, and still more preferably 0.005≤x<0.03.

n in Formula (3) is preferably 2.0 or less, more preferably 1.0 or less. By setting the value of n to 2.0 or less, it is possible to prevent the detachment of adhered water or crystallized water at the time of resin melting during spinning, and foaming or yarn breakage.

The method for adjusting the diameter of the zirconium phosphate particles related to the first aspect is not particularly limited. For example, adjustments can be made at any stage before and after contact with a basic liquid having a pH of 9 or higher, and after contact with an acidic liquid with a pH of 6 or lower, but before contact with a basic liquid with a pH of 9 or higher, that is, α as a raw material. - It is preferable to control at the stage of producing zirconium phosphate particles.

Although the method for adjusting the diameter of the α-zirconium phosphate particles used in the present disclosure is not limited, it is preferable to adjust the diameter by synthesizing α-zirconium phosphate particles in an aqueous solution in order to obtain a target particle size distribution. When synthesized in an aqueous solution, it is easy to make the particle diameter uniform during synthesis and to obtain a sharp particle size distribution. On the other hand, when the particle diameter is prepared by grinding, the width of the particle size distribution is widened due to the mixing of fine powder or large particles, and when kneaded into fibers and used as deodorizing fibers, it is easy to cause yarn breakage during spinning.

The α-zirconium phosphate particles used in the present disclosure can be produced by a known method. Conventional techniques can be applied to the method for producing α-zirconium phosphate, and there are no restrictions on raw materials and equipment. For example, the method described in Japanese Patent No. 5545328 and Japanese Patent No. 5821258, etc. are mentioned.

As a method for producing α-zirconium phosphate particles, a method in which raw material compounds are reacted in an aqueous solution is preferable because it is easy to obtain particles having a uniform particle diameter.

For example, a method of mixing an aqueous solution of a zirconium compound with an aqueous solution containing phosphoric acid and/or a salt thereof (hereinafter also referred to as "phosphoric acid (salt)") to form a precipitate, and aging to crystallize.

Examples of the zirconium compound of the raw material for producing α-zirconium phosphate particles include zirconium nitrate, zirconium acetate, zirconium sulfate, zirconium carbonate, basic zirconium sulfate, zirconium oxysulfate, and zirconium oxychloride. Zirconium nitrate, zirconium acetate, zirconium sulfate , zirconium carbonate, basic zirconium sulfate, zirconium oxysulfate, and zirconium oxychloride are preferred, and zirconium oxychloride is more preferred in view of reactivity and economy.

Examples of the phosphoric acid (salt) of the production raw material include phosphoric acid, sodium phosphate, potassium phosphate, and ammonium phosphate, and phosphoric acid is preferable.

The reaction ratio of phosphoric acid (salt) is, for example, 2 or more, preferably 2.05 or more, and more preferably 2.1 or more, as a content molar ratio with respect to the zirconium compound.

The reaction ratio of phosphoric acid (salt) may be excessive with respect to the zirconium compound, but considering the conductivity of the supernatant at the time of washing with water after synthesis, from the viewpoint of improving the efficiency of the washing process, the molar ratio is, for example, 3 or less and 2.9 or less. It is preferable and 2.6 or less is more preferable.

In the production of α-zirconium phosphate particles, it is preferable to add dicarboxylic acid (may be in the form of a hydrate) or a salt thereof to the reaction system, and examples thereof include oxalic acid, malonic acid and succinic acid, and salts thereof. can Among them, it is preferable to add oxalic acid or a salt thereof because α-zirconium phosphate can be produced more quickly, raw materials are less likely to be wasted, and can be efficiently produced.

Examples of oxalic acid or salts thereof in this case include oxalic acid dihydrate, ammonium oxalate, and ammonium hydrogen oxalate, with oxalic acid dihydrate being preferred.

The reaction ratio of oxalic acid or its salt is a molar ratio to the zirconium compound, for example, 1.0 to 3.5, more preferably 1.5 to 3.2, still more preferably 2.0 to 3.0. In the present disclosure, if the ratio is within the above range, it is preferable because production of α-zirconium phosphate becomes easy.

In the production of α-zirconium phosphate particles, an aqueous solution of a zirconium compound and an aqueous solution containing phosphoric acid (salt) are mixed and aged. Although the aging may be carried out at room temperature, it is preferable to carry out the aging at 90° C. or higher under wet normal pressure in order to speed up the aging. In addition, the synthesis may be carried out under conditions exceeding 100° C. in a pressure atmosphere higher than normal pressure, so-called hydrothermal conditions. In the case of producing α-zirconium phosphate particles under hydrothermal conditions, synthesis at 130° C. or lower is preferable from the viewpoint of production cost.

The production time of the α-zirconium phosphate particles may be any time as long as the α-zirconium phosphate particles can be synthesized. For example, α-zirconium phosphate particles can be obtained by mixing phosphoric acid (salt) and a zirconium compound to cause precipitation and then aging. The aging time varies depending on the aging temperature and is appropriately selected.

For example, in aging at 90°C, the aging time is preferably 4 hours or more. Also, even if aging is performed for 24 hours or longer, the content of α-zirconium phosphate particles tends to be at a critical point.

The synthesized α-zirconium phosphate particles are separated by further filtration, washed well with water, and then dried to obtain α-zirconium phosphate particles.

1-1-4. Method for producing zirconium phosphate particles

The method for producing zirconium phosphate particles according to the first aspect includes contacting α-zirconium phosphate particles with a basic liquid having a pH of 9 or higher, and then further contacting with an acidic liquid with a pH of 6 or lower.

The configurations of the basic liquid, the acidic liquid, and the α-zirconium phosphate particles of the raw material are as described above, and the preferred ranges are also as described above.

The temperature in the case of contacting the α-zirconium phosphate particles with a basic liquid and the temperature in the case of further contact with an acidic liquid are not particularly limited, respectively, and are usually carried out in the range of, for example, 0 to 100 ° C., but preferably It is 10-90 degreeC, More preferably, it is 15-85 degreeC.

Depending on the purpose, the contact temperature to the basic liquid and the contact temperature to the acidic liquid may be set at different temperatures.

The method of contacting the α-zirconium phosphate particles with a basic liquid and the method of contacting the acidic liquid after contacting the basic liquid are not particularly limited, and well-known methods can be applied to all of them.

For example, a method of immersing α-zirconium phosphate particles in each of these liquids, a method of immersing and stirring α-zirconium phosphate particles in each of these liquids, and spraying, dropping, or applying each of these liquids to α-zirconium phosphate particles methods and the like. Although these can be implemented individually or in combination, the method of immersing in each liquid and stirring is preferable at the point which can fully perform a contact process.

The time for contacting the α-zirconium phosphate particles with the basic liquid may be appropriately set according to the type and pH of the basic liquid to be used, the contact temperature, and the use of the finally obtained zirconium phosphate particles. The time for contacting the α-zirconium phosphate particles with the basic liquid is preferably 3 minutes to 10 hours, more preferably 15 minutes to 5 hours, still more preferably 30 minutes to 3 hours. Depending on the type and pH of the basic liquid used, the contact temperature, and the use of the finally obtained zirconium phosphate particles, the contact may be made for more than 10 hours, but if it is 10 hours or less, the production efficiency is improved, so it is economically preferable. Further, a contact treatment of 3 minutes or more is preferable because it tends to allow the α-zirconium phosphate particles to uniformly come into contact with the basic liquid.

In addition, what is necessary is just to set suitably according to the kind and pH of the acidic liquid used, contact temperature, and the use of the finally obtained zirconium phosphate particle|grains as the contact time with acidic liquid after contacting with basic liquid. The period of contact with the acidic liquid after contact with the basic liquid is preferably 3 minutes to 10 hours, more preferably 15 minutes to 5 hours, still more preferably 30 minutes to 3 hours. Depending on the type and pH of the acidic liquid used, the contact temperature, and the use of the finally obtained zirconium phosphate particles, the contact may be made for more than 10 hours, but if it is 10 hours or less, the production efficiency is improved, so it is economically preferable. Further, a contact treatment of 3 minutes or more is preferable because the α-zirconium phosphate particles tend to be uniformly contactable with the acidic liquid.

1-2. Zirconium phosphate particles related to the second aspect

For the zirconium phosphate particles according to the second aspect, 10 mg of the zirconium phosphate particles and 3 L of air containing 1000 ppm ammonia gas are placed in a test bag at room temperature and normal pressure, and the test bag containing the zirconium phosphate particles is left for 10 minutes. It is a zirconium phosphate particle whose ammonia gas reduction rate (X; unit %) represented by Formula (1) below is 50% or more.

X={(A ₀ -A ₁ )/A ₀ )}×100 (1)

[In Equation (1), A ₀ means the ammonia gas concentration of the test bag containing no zirconium phosphate particles, and A ₁ means the ammonia gas concentration of the test bag containing zirconium phosphate particles.]

The zirconium phosphate particles according to the second aspect preferably have an ammonia gas reduction rate of 55% or more, more preferably 60% or more, as expressed by the formula (1) after being allowed to stand for 10 minutes.

The zirconium phosphate particles according to the second aspect are the ammonia gas represented by the above formula (1) after putting 10 mg of zirconium phosphate particles and 3 L of air containing 1000 ppm ammonia gas into a test bag at room temperature and normal pressure and leaving it for 5 minutes. The reduction rate (X; unit %) is preferably 40% or more, more preferably 50% or more, and still more preferably 55% or more.

The material of the test bag used to determine the ammonia gas reduction rate in the present disclosure is not particularly limited, and known ones can be used. Examples thereof include polyvinyl alcohol, polyvinylidene fluoride, polyvinyl fluoride, ethylene tetrafluoride/hexafluoropropylene copolymer, and polyester.

As the method for detecting the concentration of a basic gas such as ammonia in the present disclosure, a known method can be applied and is not particularly limited. For example, the concentration of ammonia gas can be measured using a gas sampler and a detector tube. Specifically, a detection tube for ammonia gas detection with a syringe needle set on a gas sampler is attached, inserted into a test bag, ammonia gas is sucked in by the suction force of the gas sampler and adsorbed to the detection tube, and the concentration is determined from the color change of the detection tube. It can be measured by reading the value of

1-2-1. Method for producing zirconium phosphate particles

The manufacturing method of the zirconium phosphate particle concerning a 2nd aspect is not specifically limited. For example, you may manufacture by the manufacturing method of the zirconium phosphate particle concerning the 1st aspect mentioned above.

1-3. median diameter

The median diameter of the primary particles of the zirconium phosphate particles of the present disclosure (hereinafter, simply referred to as 'particle diameter') is preferably 0.1 to 10.0 μm, more preferably 0.2 to 3.0 μm, still more preferably 0.2 to 1.5 μm. is μm. It is preferable that the median diameter of the primary particles is 0.2 to 1.5 μm because the number of particles is larger when kneaded into fibers and the deodorizing effect is more likely to occur. In addition, when the median diameter of the primary particles is 0.1 μm or more, aggregation becomes difficult and it is difficult to cause yarn breakage during spinning, so it is preferable.

The particle diameter in the present disclosure represents a value obtained by measuring with a laser diffraction particle size distribution analyzer and analyzing the result on a volume basis.

The method for adjusting the diameter of the zirconium phosphate particles of the present disclosure is not particularly limited. For example, it can be adjusted in the manufacturing method of the zirconium phosphate particle|grains mentioned above.

1-4. reduction in drying

The high-speed deodorizing type zirconium phosphate particles of the present disclosure preferably have a drying loss (Y; unit weight%) of 5.0% by weight or less after heating at 150 ° C. for 2 hours under normal pressure, and more preferably is 3.0% by weight or less, more preferably 1.0% by weight or less.

By setting the drying reduction amount to 5.0% by weight or less, foaming and hydrolysis of the resin can be reduced during preparation of a deodorant resin composition containing high-speed deodorant type zirconium phosphate particles or a master batch of deodorant fibers, which is preferable.

Y={(B ₀ -B ₁ )/B ₀ ｝×100 (2)

[In Formula (2), B ₀ means the weight of zirconium phosphate particles before heating, and B ₁ means the weight of zirconium phosphate particles after heating.]

2. Usage

The zirconium phosphate particles of the present disclosure can be used for a variety of applications.

In particular, since the zirconium phosphate particles of the present disclosure have a high basic gas adsorption rate, they can be preferably used as a basic gas adsorbent.

In addition, the zirconium phosphate particles of the present disclosure can be preferably used as a deodorant, and can be more preferably used as a basic gas deodorant.

As the basic gas, ammonia that causes odor, etc., alkyl amines such as trimethylamine and dimethylamine, nitrogen-containing heterocyclic aromatic compounds such as pyridine, heterocyclic amines such as piperidine, and aromatic amines such as aniline and hydrazines.

Further, as the basic gas deodorant, it can be suitably used as a basic gas deodorant for textiles and a basic gas deodorant for textile kneading.

The specific usage method is detailed below.

3. Basic gas deodorizing composition

The high-speed deodorizing type zirconium phosphate particles of the present disclosure can be used as a basic gas deodorizing composition by appropriately mixing with a well-known binder, dispersant, oil agent, solvent, or the like. By using these, a basic gas deodorant can be electrodeposited on fibers, filters, fabrics and sheets to impart deodorizing properties.

The binder is not particularly limited, and known binders can be used. For example, it is a component for adhering the deodorant containing the zirconium phosphate particles of the present disclosure to a base material such as fibers in the production of a deodorant product, preferably. It is a high molecular compound, and may be any of a synthetic high molecular compound, a semisynthetic high molecular compound, and a natural high molecular compound.

Resins, polysaccharides, etc. are mentioned as a high molecular compound, Preferably it is a resin. In addition, one type or two or more types of binders may be included in the basic gas deodorizing composition of the present disclosure. The resin may be either a water-soluble resin or a water-insoluble resin, and is an ethylene/vinyl acetate copolymer or a modified product thereof (eg, an acid-modified product), an ethylene/vinyl chloride copolymer, or a vinyl chloride/vinyl acetate copolymer. , polyvinyl acetate, polyvinyl chloride, modified olefin resin (for example, chlorinated polyolefin, etc.), polyvinyl alcohol, alkyl cellulose, carboxyalkyl cellulose, carboxyalkyl hydroxyalkyl cellulose, polyacrylic acid, polyacrylate, acrylic resin, Polyester resin, urethane resin, styrene/butadiene copolymer, styrene/isoprene copolymer, styrene/butadiene/styrene block copolymer, styrene/ethylene/butylene/styrene block copolymer, styrene/ethylene/propylene/styrene block copolymer , hydrogenated styrene/butadiene/styrene block copolymers, hydrogenated styrene/ethylene/butylene/styrene block copolymers, hydrogenated styrene/ethylene/propylene/styrene block copolymers, and styrene/maleic anhydride copolymers. can

The dispersing agent is not particularly limited, and known ones can be used. For example, any one of anionic surfactants, cationic surfactants, cationic surfactants, and nonionic surfactants may be used, and two or more kinds may be used. may be combined Among these, from the viewpoint of the dispersibility of zirconium phosphate particles, anionic surfactants and nonionic surfactants are particularly preferred. Preferred surfactants that may be contained in the composition for deodorizing processing of basic gases of the present disclosure may be either an anionic surfactant or a nonionic surfactant, or both.

The composition for basic gas deodorizing processing of the present disclosure may contain a medium. Although there is no limitation in particular as a medium, For example, only water or a liquid mixture of water and a water-soluble organic solvent is mentioned, and water is preferable.

Examples of the water-soluble organic solvent include lower alcohols such as methanol, ethanol and 2-propanol.

4. Basic gas deodorizing resin composition

The high-speed deodorizing type zirconium phosphate particles of the present disclosure can be used as a basic gas deodorizing resin composition by mixing with a resin. Examples of the resin include polypropylene, polyethylene, acrylonitrile/butadiene/styrene (ABS), polyester, polyurethane, nylon, polystyrene, polycarbonate, acrylic resin, and vinyl chloride resin. However, those resins are not limited to these resins. not.

The method for producing the basic gas deodorizing resin composition is not particularly limited.

For example, you may manufacture by the method including mixing the zirconium phosphate particle obtained by the manufacturing method of the zirconium phosphate particle mentioned above, and resin.

In addition, after contacting the zirconium phosphate particles with a basic liquid of pH 9 or higher, further contact with an acidic liquid of pH 6 or less to obtain liquid-treated zirconium phosphate particles, mixing the liquid-treated zirconium phosphate particles and a resin. It may be manufactured by the method.

The method of mixing the zirconium phosphate particles and the resin is not particularly limited, but from the viewpoint of imparting durability and abrasion resistance so that the zirconium phosphate does not fall off from the resin and maintaining the deodorizing performance, it is preferable to knead the zirconium phosphate particles into the resin.

5. Basic gas deodorizing fiber

The basic gas deodorizing fiber of the present disclosure is not particularly limited as long as it includes the zirconium phosphate particles of the present disclosure or the basic gas deodorant containing the same.

As a method for manufacturing the basic gas deodorizing fiber of the present disclosure, a conventional method may be used.

For example, a method of kneading and spinning the basic gas deodorant of the present disclosure into fibers, a method of coating the spun fibers with a composition for basic gas deodorant processing containing the basic gas deodorant of the present disclosure, and the like.

There is no restriction on the resin for fibers that can be used for the processing of the basic gas deodorant of the present disclosure, and all known chemical fibers can be used. As this preferable specific example, polyester, polyurethane, nylon, rayon, an acrylic resin, aramid, vinylon, polyethylene, and polypropylene etc. are mentioned, for example. Among them, polyurethane, polyester, nylon, acrylic resin and polyethylene are preferred. These resins may be homopolymers or copolymers. In the case of a copolymer, the polymerization ratio of each copolymerization component is not particularly limited.

Any polyurethane may be used as long as it contains a polymer diol and diisocyanate as starting materials, and is not particularly limited. In addition, the synthesis method is not specifically limited, either.

In addition, although polyester is not specifically limited, For example, polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, and polybutylene terephthalate are preferable.

The basic gas deodorant of the present disclosure can be preferably used as a deodorant for fabric kneading.

In this case, as a specific method for producing the basic gas deodorizing fiber, a method in which the deodorant of the present disclosure is kneaded into a melted liquid resin for fibers or a resin solution for fibers dissolved in a solvent and then spun, and a basic gas deodorant is contained in a high concentration. After processing into a master batch resin to be used, a method of mixing and melting with a resin for fibers and spinning, and the like are exemplified.

The ratio of the basic gas deodorant of the present disclosure to be contained in the resin for textiles is not particularly limited. In general, if the content is increased, the deodorizing property can be strongly exerted and maintained for a long period of time, but from the point of view of not having a large difference in the deodorizing effect or reducing the strength of the resin, and economical efficiency, even if the content exceeds a certain level, preferably It is 0.1 to 5.0 parts by weight, more preferably 0.5 to 2.0 parts by weight per 100 parts by weight of the resin.

In the method for producing a basic gas deodorizing resin composition containing zirconium phosphate particles of the present disclosure, the resin containing zirconium phosphate particles is brought into contact with a basic liquid having a pH of 9 or higher and then brought into contact with an acidic liquid having a pH of 6 or lower.

In the method for producing a basic gas deodorizing fiber containing zirconium phosphate particles of the present disclosure, the fiber containing zirconium phosphate particles is brought into contact with a basic liquid having a pH of 9 or higher and then brought into contact with an acidic liquid having a pH of 6 or less.

In the present invention, after contacting zirconium phosphate with a basic liquid of pH 9 or higher, further contact with an acidic liquid of pH 6 or less may be made in direct contact with zirconium phosphate, or by contacting a kneaded material such as resin or fiber, Even if the liquid penetrates into the resin or fiber, and the basic liquid and the acidic liquid contact the zirconium phosphate in the resin or fiber, the same conceptual scope and the same effect are exhibited.

As the zirconium phosphate particles, after contacting α-zirconium phosphate particles and α-zirconium phosphate particles with a basic liquid having a pH of 9 or higher, zirconium phosphate particles obtained by further contacting an acidic liquid with a pH of 6 or lower, β-zirconium phosphate particles, Zirconium phosphate having basic gas adsorption ability, such as γ-zirconium phosphate particle|grains and amorphous zirconium phosphate particle|grains, is mentioned. Preferably, after contacting α-zirconium phosphate particles and α-zirconium phosphate particles with a basic liquid having a pH of 9 or higher, zirconium phosphate particles obtained by further contacting an acidic liquid with a pH of 6 or lower are mentioned. More preferably, zirconium phosphate particles obtained by contacting α-zirconium phosphate particles with a basic liquid having a pH of 9 or higher and further contacting an acidic liquid with a pH of 6 or lower are used. That is, in the case of using zirconium phosphate particles, which are liquid treated products of the α-zirconium phosphate particles, the second liquid treatment is performed on the resin or fiber containing the zirconium phosphate particles. The second liquid treatment may be a treatment substantially including a dyeing treatment or the like.

The basic gas deodorizing resin composition and basic gas deodorizing fibers containing zirconium phosphate particles have poor deodorizing properties due to deterioration in adsorption performance of basic gas after, for example, contact treatment with a basic liquid in a fiber manufacturing process such as dyeing treatment. There are cases where it becomes, and furthermore, does not appear. In contrast, as in the present disclosure, after the contact treatment with the basic liquid described above, further contact treatment with an acidic liquid not only exhibits deodorizing properties, but also after the contact treatment with the basic liquid according to the present disclosure, further acidic A basic gas deodorizing resin composition and basic gas deodorizing fibers having an improved basic gas deodorizing rate compared to the basic gas deodorizing resin composition and basic gas deodorizing fibers before contact with a liquid are provided.

6. Additives

The basic gas deodorant containing high-speed deodorizing type zirconium phosphate particles, the basic gas deodorant for textiles, the basic gas deodorizing composition, the basic gas deodorizing resin composition, and the basic gas deodorizing fiber of the present disclosure may contain appropriate additives.

The additive is not particularly limited, and a thickener, other well-known deodorants such as acid gas deodorizers, basic gas deodorants, sulfur-based gas deodorants, aldehyde-based gas deodorants, ketone-based gas deodorants, antibacterial agents, antifungal agents, antiviral processing agents, anti-allergen agents, anti-foaming agents, colorants, preservatives, viscosity modifiers and fragrances; and the like.

In addition, other well-known deodorants do not include the basic gas deodorant of the present disclosure.

The thickener is not particularly limited, and known ones can be used. For example, polysaccharides and the like can be used. Specific examples include xanthan gum, alginates, gum arabic, starch, tamarind seed gum, guar gum, and carboxymethyl cellulose. etc. can be mentioned.

Other deodorants may be blended in a type and ratio that do not degrade the deodorizing performance of the basic gas of the obtained deodorant product.

Examples of compounds that cause odor and the like include basic gases such as ammonia gas and trimethylamine; acidic gases such as acetic acid and isovaleric acid; aldehyde-based gases such as formaldehyde, acetaldehyde, and nonenal; and sulfur-based gases such as hydrogen sulfide and methyl mercaptan. Other deodorants having deodorizing performance against these may be contained.

Examples of deodorants for basic gases include zeolite, Al ₂ O ₃ , SiO ₂ , MgO, CaO, SrO, BaO, ZrO ₂ , TiO ₂ , WO ₂ , CeO ₂ , Li ₂ O, Na ₂ O and K ₂ O. and amorphous composite oxides.

Examples of the acid gas deodorant include hydrotalcite-based compounds such as zirconium hydroxide, zirconium oxide, and magnesium-aluminum hydrotalcite.

As deodorants for aldehyde-based gases, hydrazine-based compounds such as adipic acid dihydrazide, carbohydrazide, succinic acid dihydrazide and oxalic acid dihydrazide, aminoguanidine hydrochloride, aminoguanidine sulfate, and aminoguanidine bicarbonate, etc. amino A guanidine salt etc. are mentioned.

Examples of the deodorant for sulfur-based gas include copper silicate, copper phosphate zirconium hydrate, zinc oxide, aluminum zinc oxide, zinc silicate, aluminum zinc silicate, layered aluminosilicate zinc, and the like.

The deodorant resin composition using the deodorant of the present disclosure can be used in various fields requiring deodorizing properties, for example, daily necessities such as trash cans, triangular corners, wraps, sponges, refrigerators, air purifier filters, air conditioner filters, etc. Electrical appliances, wall coverings, toilet seats, toilet seats, kitchen counters, ventilation fan filters, housing construction materials products such as paints, textile products such as clothing, bedding, curtains, mats, shoes, stockings, socks, pet products and care products, and many resins. can be used in the product.

Deodorant fibers using the deodorant of the present disclosure can be used in various fields requiring deodorizing properties, such as underwear, stockings, socks, duvets, duvet covers, cushions, blankets, carpets, curtains, sofas, and car seats. It can be used for many textile products, such as air filters and nursing care clothing.

Example

Next, the present disclosure will be specifically described based on Examples and Comparative Examples, but the present disclosure is not limited to the following Examples.

<Production Example 1> (Production of α-zirconium phosphate)

1345 mL of deionized water and 135 g of 35% hydrochloric acid were placed in a 2 L round bottom flask, 225 g of a 20% aqueous solution of zirconium oxychloride octahydrate containing 0.18% by weight of hafnium was added, and then 93 g of oxalic acid dihydrate was added and dissolved. 101 g of 75% phosphoric acid was added to this solution while stirring well. After heating this to 98 degreeC over 2 hours, it was refluxed stirring for 12 hours. After cooling the reaction system, the resulting precipitate was collected by filtration, washed well, and then dried at 105°C under normal pressure to obtain zirconium phosphate. This was pulverized with a rotor speed mill (16000 rpm, sieve opening 80 μm). Powder X-ray diffraction measurement and fluorescence X-ray analysis were performed on the obtained zirconium phosphate, and it was confirmed that it was α-zirconium phosphate.

Fluorescence X-ray analysis and simultaneous _{thermogravimetric} and differential thermal measurement ( _{TG - DTA} ) of this _{α -} zirconium phosphate were performed. It was 0.89 μm.

Powder X-ray diffraction, fluorescence X-ray analysis, TG-DTA, and particle diameter (median diameter) measurement conditions and measurement methods are described below.

<Powder X-ray diffraction>

As the X-ray diffractometer, D8 ADVANCE manufactured by BRUKER was used. An X-ray diffraction diagram was obtained using CuKα generated at an applied voltage of 40 kV and a current value of 40 mA using a Cu encapsulated X-ray source. Detailed measurement conditions are as follows.

X-ray source: Encapsulated X-ray source (Cu source), 0.4×12 mm ² , Long Fine Focus

Rating: 2.2kW

Power used: 40 kV-40 mA (1.6 kW)

Goniometer radius: 280 mm

Sample stage: FlipStick_Twin_Twin-XE

Measurement range 2θ: 5° to 55°

Step Width: 0.02°

Step time: 0.05 sec/step

Incidence side solar slit: 2.5°

Anti-scatter slit: 10.5 mm

Curvature: 1.00

Detector: LYNXEYE XE

Detector slit width: 5.758 mm

Detector window width: 2.9°

<Fluorescent X-ray analysis>

Fluorescence X-ray analysis was measured under the following conditions.

Measuring instrument: manufactured by Rigaku 　ZSX 　Primus Ⅱ

Measuring conditions

Measured elements: C to U (F, Cl, Br, I measured on time, BG 4 sec, peak 8 sec)

Analytical diameter: 20 mm

Number of measurements: measured in n2

Sample processing: A sample was pressure-molded into a pellet shape using a tablet molding machine, and subjected to measurement.

Translate

Software：ZSX version 7.49

Model: Bulk

<TG-DTA>

TG-DTA was measured under the following conditions.

Measuring instrument: TG/DTA 6300 manufactured by Hitachi High-Tech Science

Measurement method: Put 7 to 8 mg of the sample in an Al pan, set, raise the temperature to 600 ° C at 20 ° C / min, take the amount of moisture (adhered water) as the weight loss from room temperature to 100 ° C, and measure from 100 ° C to 250 ° C. Loss was evaluated as the number of crystals.

<Particle diameter (median diameter) measurement>

The particle diameter of the deodorant was measured with a laser diffraction type particle size distribution analyzer "Master Sizer-2000" manufactured by Marban, and the results were analyzed on a volumetric basis. The deodorant dispersion to which the deodorant was added was dispersed by ultrasonic wave and the refractive index was measured as 2.4.

<Example 1>

[Use of sodium hydroxide: 1/4 molar ratio to the P-OH group of α-zirconium phosphate, bath ratio: α-zirconium phosphate/NaOH aqueous solution = 1/20 weight ratio]

After putting 3 g of α-zirconium phosphate and 3 g of pure water obtained in Preparation Example 1 in a 100 mL beaker and stirring with a stirrer, 57 g of an aqueous sodium hydroxide solution having the pH adjusted to 12.9 (1 for the P-OH group of α-zirconium phosphate) /4 molar ratio) was added, and after stirring at 80°C for 1 hour, it was filtered. Then, after filtration and washing until the electrical conductivity of the filtrate is 100 μS / cm or less, the obtained zirconium phosphate is dried under normal pressure at 120 ° C. for 2 hours, and pulverized with an agate mortar, and basic liquid treated zirconium phosphate particles (A -1) was obtained. Next, put 200 g of 1 N aqueous solution of nitric acid (pH1) in a 200 mL beaker, add 1.8 g of basic liquid treated zirconium phosphate thereto, stir at 80 ° C. for 2 hours, and conduct electrical conductivity of the filtrate in the same manner as above. After filtration and washing until 100 μS/cm or less, the resulting zirconium phosphate was dried under normal pressure at 120° C. for 2 hours and pulverized with an agate mortar to obtain acidic liquid-treated zirconium phosphate particles (A-2). In addition, at the time of adjusting pH, the HORIBA SD-51 pH meter was used.

The median diameter of A-2 was measured according to the above method, and the drying loss fraction was measured according to the method shown in (1) below. These results are shown in Table 1.

In addition, the performance of A-2 as a deodorant was measured according to the method shown in (2) below. The results are shown in Table 1.

(1) Measurement of drying reduction fraction (%)

The drying reduction fraction of the deodorant particles was measured according to the first method of 4.1.1 (1) of JIS 　K 0067: 1992 (Test method for weight loss and residual content of chemical products). After leaving the deodorant particles in a room with a temperature of 25 ° C and a humidity of 50% for 24 hours, they were heated at 150 ° C. under normal pressure for 2 hours, and the weight before and after heating was measured. Y; unit weight %) was calculated.

Y={(B ₀ -B ₁ )/B ₀ ｝×100 (2)

[In Formula (2), B ₀ means the weight of zirconium phosphate particles (deodorant) before heating, and B ₁ means the weight of zirconium phosphate particles (deodorant) after heating.]

(2) Deodorization test

As a deodorization test, deodorization of odor components was evaluated by an instrument test as follows.

First, 10 mg of zirconium phosphate particles are placed in a test bag (Tedler bag), and ammonia gas and dry air are injected thereto to set the ammonia gas concentration in the test bag to 1000 ppm and the gas volume to 3 L, then, The ammonia gas reduction rate (X; unit %) in the test bag after being allowed to stand at room temperature and pressure for 10 minutes was calculated by the following formula (1). In addition, in order to calculate the ammonia gas reduction rate, a test bag containing no zirconium phosphate particles was also prepared, and the ammonia gas concentration after 10 minutes was measured.

X={(A ₀ -A ₁ )/A ₀ )}×100 (1)

[In Equation (1), A ₀ means the ammonia gas concentration of the test bag containing no zirconium phosphate particles, and A ₁ means the ammonia gas concentration of the test bag containing zirconium phosphate particles.]

<Example 2>

[Use of sodium hydroxide: 1/3 molar ratio to the P-OH group of α-zirconium phosphate, bath ratio: α-zirconium phosphate/NaOH aqueous solution = 1/20 weight ratio]

Basic liquid treated zirconium phosphate particles (B-1) and acidic liquid treated zirconium phosphate particles (B-2).

The median diameter, reduced drying fraction, and deodorizing performance of B-2 were measured and evaluated in the same manner as in Example 1. Table 1 shows these results.

<Example 3>

[Amount of sodium hydroxide: 1/2 molar ratio to the P-OH group of α-zirconium phosphate, bath ratio: α-zirconium phosphate/NaOH aqueous solution = 1/20 weight ratio]

Basic liquid treated zirconium phosphate particles (C-1) and acidic liquid treated zirconium phosphate particles (C-2).

The median diameter, reduced drying fraction, and deodorizing performance of C-2 were measured and evaluated in the same manner as in Example 1. Table 1 shows these results.

<Example 4>

[Amount of sodium hydroxide: 1/1.5 molar ratio to the P-OH group of α-zirconium phosphate, bath ratio: α-zirconium phosphate/NaOH aqueous solution = 1/20 weight ratio]

Basic liquid-treated zirconium phosphate particles (D-1) in the same manner as in Example 1 except that 57 g of an aqueous sodium hydroxide solution having the pH adjusted to 13.4 (1/1.5 molar ratio with respect to the P-OH group of α-zirconium phosphate) was used and acidic liquid treated zirconium phosphate particles (D-2).

The median diameter, reduced drying fraction, and deodorizing performance of D-2 were measured and evaluated in the same manner as in Example 1. Table 1 shows these results.

<Example 5>

[Amount of sodium hydroxide: 1/1 molar ratio to the P-OH group of α-zirconium phosphate, bath ratio: α-zirconium phosphate/NaOH aqueous solution = 1/20 weight ratio]

Basic liquid treated zirconium phosphate particles (E-1) and acidic liquid treated zirconium phosphate particles (E-2).

The median diameter, reduced drying fraction, and deodorizing performance of E-2 were measured and evaluated in the same manner as in Example 1. Table 1 shows these results.

<Example 6>

[Amount of sodium hydroxide: 1/3 molar ratio to the P-OH group of α-zirconium phosphate, bath ratio: α-zirconium phosphate/NaOH aqueous solution = 1/5 weight ratio]

Examples except for using 9 g of α-zirconium phosphate obtained in Production Example 1, 9 g of pure water, and 36 g of aqueous sodium hydroxide solution having the pH adjusted to 13.8 (1/3 molar ratio to the P-OH group of α-zirconium phosphate) In the same manner as in 1, basic liquid treated zirconium phosphate particles (F-1) and acidic liquid treated zirconium phosphate particles (F-2) were obtained.

The median diameter, reduced drying fraction, and deodorizing performance of F-2 were measured and evaluated in the same manner as in Example 1. Table 1 shows these results.

<Example 7>

[Amount of sodium hydroxide: 1/2 molar ratio to the P-OH group of α-zirconium phosphate, bath ratio: α-zirconium phosphate/NaOH aqueous solution = 1/5 weight ratio]

Basic liquid treated zirconium phosphate particles (G-1) and acidic liquid treated zirconium phosphate particles (G-2).

The median diameter, reduced drying fraction, and deodorizing performance of G-2 were measured and evaluated in the same manner as in Example 1. Table 1 shows these results.

<Example 8>

[Amount of sodium hydroxide: 1/1.5 molar ratio to the P-OH group of α-zirconium phosphate, bath ratio: α-zirconium phosphate/NaOH aqueous solution = 1/5 weight ratio]

Basic liquid-treated zirconium phosphate particles (H-1) in the same manner as in Example 6 except that 36 g of an aqueous solution of sodium hydroxide adjusted to pH 14.0 (1/1.5 molar ratio to the α-zirconium phosphate P-OH group) was used and acidic liquid treated zirconium phosphate particles (H-2).

The median diameter, reduced drying fraction, and deodorizing performance of H-2 were measured and evaluated in the same manner as in Example 1. Table 1 shows these results.

<Comparative Example 1>

[α-zirconium phosphate]

The median diameter, reduced drying fraction, and deodorizing performance of the α-zirconium phosphate particles obtained in Production Example 1 were measured and evaluated in the same manner as in Example 1. Table 1 shows these results.

<Example 9>

3% by weight of acid-treated zirconium phosphate (G-2) obtained in Example 7 was mixed with 97% by weight of a polyester resin (MA-2101M manufactured by Unitica Co., Ltd.) dried at 150 ° C. for 12 hours, and set at 270 ° C. It was put into a fully automatic injection molding machine (manufactured by Meiki Seisakusho, model: M-50A II-DM) to produce an injection molding plate of 11 cm x 11 cm x 1 mm. Then, this plate was pulverized with a wonder blender (manufactured by Osaka Chemical Co., Ltd., model: WB-1) so that the median diameter was 200 μm ± 100 μm, and a zirconium phosphate kneaded resin composition A was obtained. The deodorizing performance was evaluated according to the method shown in (3) Deodorizing Test-2 described later. The results are shown in Table 2.

<Comparative Example 2>

3% by weight of α-zirconium phosphate used in Comparative Example 1 was mixed with 97% by weight of a polyester resin (MA-2101M manufactured by Unitica Co., Ltd.) dried at 150° C. for 12 hours, and kneaded with zirconium phosphate in the same manner as in Example 9. Inclusion resin composition B was obtained. The deodorizing performance was evaluated according to the method shown in (3) Deodorizing Test-2 described later. The results are shown in Table 2.

(3) Deodorization test-2

Put 2.4 g of the resin composition containing zirconium phosphate dough into a test bag (Tedler bag), inject dry air and ammonia gas into it, set the ammonia gas concentration in the test bag to 100 ppm, and set the gas capacity to 3 L, It was allowed to stand for 1 hour at room temperature and normal pressure. The ammonia gas reduction rate in the test bag after standing was calculated according to the above-mentioned formula (1). In addition, here, A ₀ in Formula (1) means the ammonia gas concentration of the test bag containing no zirconium phosphate dough-containing resin composition, and A ₁ is the ammonia gas concentration of the test bag containing the zirconium phosphate dough-containing resin composition. it means.

As for the indication of Japanese Patent Application No. 2020-044208 for which it applied on March 13, 2020, the whole is taken in into this specification as a reference.

All documents, patent applications, and technical standards cited herein are incorporated herein by reference to the same extent as if each document, patent application, and technical standard were specifically and specifically stated to be incorporated by reference.

The zirconium phosphate particles of the present disclosure can be preferably used for a deodorant, and the deodorant has a high adsorption rate to basic gas such as ammonia and is particularly excellent in deodorizing performance of ammonia. and deodorant fibers.

In addition, the manufacturing method of the zirconium phosphate particles of the present disclosure may provide a manufacturing method capable of improving the deodorizing performance.

Claims (21)

Zirconium phosphate particles obtained by bringing the α-zirconium phosphate particles into contact with a basic liquid having a pH of 9 or higher and further contacting an acidic liquid with a pH of 6 or lower. According to claim 1,
The zirconium phosphate particle, wherein the basic liquid contains an alkali metal and/or an alkaline earth metal. 10 mg of zirconium phosphate particles and 3 L of air containing 1000 ppm of ammonia gas are placed in a test bag at room temperature and normal pressure, and the ammonia gas reduction rate expressed by the following formula (1) in the test bag containing the zirconium phosphate particles after leaving it for 10 minutes Zirconium phosphate particles in which (X; unit %) is 50% or more.
X={(A ₀ -A ₁ )/A ₀ )}×100 (1)
[In Equation (1), A ₀ means the ammonia gas concentration of the test bag containing no zirconium phosphate particles, and A ₁ means the ammonia gas concentration of the test bag containing zirconium phosphate particles.] According to any one of claims 1 to 3,
Zirconium phosphate particles with a primary particle median diameter of 0.1 to 10 μm. According to any one of claims 1 to 4,
Zirconium phosphate particles having a reduced drying fraction (Y; unit weight%) of 5.0% by weight or less represented by the following formula (2) after heating at 150 ° C. for 2 hours.
Y={(B ₀ -B ₁ )/B ₀ ｝×100 (2)
[In Formula (2), B ₀ means the weight of zirconium phosphate particles before heating, and B ₁ means the weight of zirconium phosphate particles after heating.] A basic gas deodorizer comprising the zirconium phosphate particles according to any one of claims 1 to 5. A basic gas deodorizer for textiles comprising the zirconium phosphate particles according to any one of claims 1 to 5. A basic gas deodorant for fiber kneading comprising the zirconium phosphate particles according to any one of claims 1 to 5. A composition for basic gas deodorizing processing comprising the zirconium phosphate particles according to any one of claims 1 to 5. A basic gas deodorizing resin composition comprising the zirconium phosphate particles according to any one of claims 1 to 5. A basic gas deodorizing fiber comprising the zirconium phosphate particles according to any one of claims 1 to 5. According to claim 11,
A basic gas deodorizing fiber comprising at least one fiber selected from the group consisting of polyester, polyurethane, nylon, rayon, cotton, acrylic, aramid, vinylon, polyethylene and polypropylene. According to any one of claims 1 to 5,
A method for producing zirconium phosphate particles comprising contacting α-zirconium phosphate particles with a basic liquid having a pH of 9 or higher and further contacting an acidic liquid with a pH of 6 or lower. According to claim 13,
The method for producing zirconium phosphate particles, wherein the basic liquid contains an alkali metal and/or an alkaline earth metal. A method for producing a basic gas deodorizing resin composition comprising mixing zirconium phosphate particles obtained by the production method according to claim 13 or 14 and a resin. After contacting the zirconium phosphate particles with a basic liquid of pH 9 or higher, further contacting with an acidic liquid of pH 6 or less to obtain liquid-treated zirconium phosphate particles;
A method for producing a basic gas deodorizing resin composition comprising mixing the liquid treated zirconium phosphate particles and a resin. A method for producing basic gas deodorizing fibers, comprising spinning the basic gas deodorizing resin composition obtained by the production method according to claim 15 or 16. A method for producing a basic gas deodorizing resin composition comprising contacting a resin containing zirconium phosphate particles with a basic liquid having a pH of 9 or higher and then contacting an acidic liquid with a pH of 6 or lower. According to claim 18,
A method for producing a basic gas deodorizing resin composition, wherein the zirconium phosphate particles are those according to any one of claims 1 to 5. A method for producing a basic gas deodorizing fiber comprising contacting a fiber containing zirconium phosphate particles with a basic liquid having a pH of 9 or higher and then contacting an acidic liquid with a pH of 6 or lower. According to claim 20,
A method for producing basic gas deodorizing fibers, wherein the zirconium phosphate particles are those according to any one of claims 1 to 5.